The invention relates to novel thienylsulphonylamino(thio)carbonyl compounds, to a plurality of processes and novel intermediates for their preparation and to their use as herbicides.
It is already known that certain suiphonylaminocarbonyl compounds have herbicidal properties (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266, DE 4029753). However, the activity of these compounds is not in all respects satisfactory.
This invention, accordingly, provides the novel thienylsulphonylamino(thio)carbonyl compounds of the general formula (I), 
in which
Q represents oxygen or sulphur,
R1 represents cyano, halogen or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy or alkinyloxy having in each case up to 6 carbon atoms,
R2 represents cyano, halogen or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkeinyloxy or alkinyloxy having in each case up to 6 carbon atoms, and
R3 represents in each case optionally substituted heterocyclyl having 5 ring members, at least one of which represents oxygen, sulphur or nitrogen and one to three others may represent nitrogen,
and salts of compounds of the formula (I).
The novel thienylsulphonylamino(thio)carbonyl compounds of the general formula (I) are obtained when
(a) sulphonamides of the general formula (II) 
xe2x80x83in which
R1 and R2 are each as defined above,
are reacted with (thio)carboxylic acid derivatives of the general formula (III) 
xe2x80x83in which
Q and R3 are each as defined above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,
or when
(b) sulphonyl iso(thio)cyanates of the general formula (IV) 
xe2x80x83in which
Q, R1 and R2 are each as defined above,
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x88x921xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3xe2x88x921 represents optionally substituted heterocyclyl having 5 ring members, at least one of which represents greater than Nxe2x80x94H,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
or when
(c) sulphonyl chlorides of the general formula (VI) 
xe2x80x83in which
R1 and R2 are each as defined above,
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x88x921xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3xe2x88x921 is as defined above under (b),
and metal (thio)cyanates of the general formula (VII)
MQCNxe2x80x83xe2x80x83(VII)
xe2x80x83in which
Q is as defined above and
M represents a metal equivalent,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
or when
(d) sulphonyl chlorides of the general formula (VI) 
xe2x80x83in which
R1 and R2 are each as defined above,
are reacted with (thio)carboxamides of the general formula (VIII) 
xe2x80x83in which
Q and R3 are each as defined above under formula (I),
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,
or when
(e) sulphonylamino(thio)carbonyl compounds of the general formula (IX) 
xe2x80x83in which
Q, R1 and R2 are each as defined above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x88x921xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3xe2x88x921 is as defined above under (b),
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent,
and the compounds of the formula (I) obtained by the processes (a), (b), (c), (d) or (e) are, if appropriate, converted into salts by customary methods.
According to their nature, the processes (b), (c) and (e) are only suitable for preparing those compounds of the formula (I) in which R3 represents R3xe2x88x921.
The novel thienylsulphonylamino(thio)carbonyl compounds of the general formula (I) have strong herbicidal activity.
The invention preferably provides compounds of the formula (I) in which
Q represents oxygen or sulphur,
R1 represents cyano, halogen, represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkyl, represents in each case optionally cyano- or halogen-substituted C2-C4-alkenyl or C2-C4-alkinyl, represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkoxy, or represents in each case optionally cyano- or halogen-substituted C2-C4-alkenyloxy or C2-C4-alkinyloxy,
R2 represents cyano, halogen, represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkyl, represents in each case optionally cyano- or halogen-substituted C2-C4-alkenyl or C2-C4-alkinyl, represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C4-alkoxy, or represents in each case optionally cyano- or halogen-substituted C2-C4-alkenyloxy or C2-C4-alkinyloxy, and
R3 represents in each case optionally substituted heterocyclyl of the formulae below 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulphur and
R4 represents hydrogen, hydroxyl, amino, cyano, represents C2-C10-alkylideneamino, represents optionally fluorine-, chlorine-, bromine-,cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents in each case optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, represents C3-C6-alkenyloxy, represents di-(C1-C4-alkyl)-amino, represents in each case optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkylamino or C3-C6-cycloalkyl-C1-C4-alkyl, or represents in each case optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl and/or C1-C4-alkoxy-substituted phenyl or phenyl-C1-C4-alkyl,
R5 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents in each case optionally fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, represents C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, represents di-(C1-C4-alkyl)-amino, represents in each case optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents in each case optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or represents in each case optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore
R6, R7 and R8 are identical or different and each represent hydrogen, cyano, fluorine, chlorine, bromine, or represent in each case optionally fluorine-, chlorine-, bromine- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl or alkylsulphonyl having in each case up to 6 carbon atoms or represent optionally cyano-, fluorine-, chlorine-, bromine or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.
The invention furthermore preferably provides sodium, potassium, magnesium, calcium ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-anunonium salts of compounds of the formula (I) in which Q, R1, R2 and R3 each have the meaning given above as being preferred.
The invention in particular provides compounds of the formula (I) in which
Q represents oxygen or sulphur,
R1 represents cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, represents in each case optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, or represents in each case optionally cyano-, fluorine- or chlorine-substituted propenyloxy, butenyloxy, propinyloxy or butinyloxy,
R2 represents cyano, fluorine, chlorine, bromine, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, represents in each case optionally cyano-, fluorine- or chlorine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, or represents in each case optionally cyano-, fluorine- or chlorine-substituted propenyloxy, butenyloxy, propinyloxy or butinyloxy, and
R3 represents in each case optionally substituted heterocyclyl of the formulae below 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulphur and
R4 represents hydrogen, hydroxyl, amino, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents in each case optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl
R5 represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propadienylthio, butenylthio, propenylamino, butenylamino, propinylamino or butenylamino, represents dimethylamino, diethylamino or dipropylamino, represents in each case optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethyl-thio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents in each case optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore
R6, R7 and R8 are identical or different and each represent hydrogen, cyano, fluorine, chlorine, bromine, or represent in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenyloxy, butenyloxy, propinyloxy, butinyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio, butenylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represent cyclopropyl.
A very particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which
Q represents oxygen or sulphur,
R1 represents methyl, ethyl, n- or i-propyl,
R2 represents methyl, ethyl, n- or i-propyl and
R3 represents optionally substituted triazolinyl of the formula below 
xe2x80x83in which
Q1 represents oxygen or sulphur and
R4 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, represents in each case optionally fluorine- or chlorine-substituted propenyl or propinyl, represents methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino, n- or i-propylamino, represents propenyloxy, represents dimethylamino or represents cyclopropyl,
R5 represents chlorine or bromine, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propinylthio, butenylthio, propenylamino, butenylamino, propinylamino or butenylamino, represents dimethylamino, diethylamino or dipropylamino, represents in each case optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclo-butyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclo-butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropyl-methylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexyl-methylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentyl-methylamino or cyclohexylmethylamino, or represents in each case optionally fluorine-, chlorine-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms.
The above mentioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, that is to say combinations between the stated preferred ranges are also possible.
Using, for example, 4-bromo-2-methyl-thiophene-3-sulphonamide and 5-ethoxy-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-thione as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following equation: 
Using, for example, 4-chloro-2-ethyl-3-thienylsulphonyl isothiocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following equation: 
Using, for example, 4-ethyl-2-methoxy-thiophene-3-sulphonyl chloride, 5-ethyl-thio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one and potassium cyanate as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following equation: 
Using, for example, 4-cyano-2-isopropyl-thiophene-3-sulphonyl chloride and 5-methyl-1,2,4-oxadiazole-3-carboxamide as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following equation: 
Using, for example, N-(4-fluoro-2-triluoromethyl-thiophen-3-yl-sulphonyl)-O-methyl-urethane and 4-methyl-5-methylthio-2,4-dihydro-311-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (e) according to the invention can be illustrated by the following equation: 
The formula (II) provides a general definition of the sulphonamides to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I). In the formula (II), R1 and R2 each preferably or in particular have those meanings which have already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1 and R2.
The starting materials of the formula (II) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel sulphonamides of the formula (II) are obtained when sulphonyl chlorides of the formula (VI) 
in which
R1 and R2 are each as defined above,
are reacted with ammonia, if appropriate in the presence of a diluent, such as, for example, water, at temperatures between 0xc2x0 C. and 50xc2x0 C. (cf. the Preparation Examples).
The sulphonyl chlorides of the formula (VI) have likewise hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel sulphonyl chlorides of the formula (VI) are obtained when corresponding amino compounds of the general formula (X) 
in which
R1 and R2 are each as defined above,
are reacted with an alkali metal nitrite, such as, for example, sodium nitrite, in the presence of hydrochloric acid at temperatures between xe2x88x9210xc2x0 C. and +10xc2x0 C. and the resulting diazonium salt solution is reacted with sulphur dioxide in the presence of a diluent, such as, for example, dichloromethane, 1,2-dichloroethane or acetic acid, and in the presence of a catalyst, such as, for example, copper(l) chloride and/or copper(II) chloride, at temperatures between xe2x88x9210xc2x0 C. and +50xc2x0 C. (cf. the Preparation Examples).
The amino compounds of the formula (X) required as precursors are known and/or can be prepared by processes known per se (cf. DE 33 03 388).
The formula (III) provides a general definition of the (thio)carboxylic acid derivatives further to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I). In the formula (III), Q and R3 each preferably or in particular have that meaning which has already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Q and R3; Z preferably represents fluorine, chlorine, bromine, C1-C4-alkoxy, phenoxy or benzyloxy, in particular represents chlorine, methoxy, ethoxy or phenoxy.
The starting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP 459244, EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
The formula (IV) provides a general definition of the sulphonyl iso(thio)cyanates to be used as starting materials in the process (b) according to the invention for preparing the compounds of the formula (I). In the formula (IV), Q, R1 and R2 each preferably or in particular have that meaning which has already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Q, R1 and R2.
The sulphonyl iso(thio)cyanates of the formula (IV) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application.
The novel sulphonyl iso(thio)cyanates of the formula (IV) are obtained when sulphonamides of the general formula (II)xe2x80x94abovexe2x80x94are reacted with phosgene and thiophosgene, respectively, if appropriate in the presence of an alkyl iso-cyanate, such as, for example, butyl isocyanate, if appropriate in the presence of a reaction auxiliary, such as, for example, diazabicyclo[2.2.2]octane, and in the presence of a diluent, such as, for example, toluene, xylene or chlorobenzene, at temperatures between 80xc2x0 C. and 150xc2x0 C. and the volatile components are distilled off under reduced pressure after the reaction has ended (cf. the Preparation Examples).
The formula (V) provides a general definition of the heterocycles to be used as starting materials in the processes (b), (c) and (e) according to the invention. In the formula (V), R3xe2x88x921 preferably represents optionally substituted triazolinyl of the formula below 
in which Q1 represents oxygen or sulphur and the radicals R4 and R5 each preferably or in particular have those meanings which have already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R4 and R5.
The starting materials of the formula (V) are known and/or can be prepared by processes known per se (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
The formula (VI) provides a general definition of the sulphonyl chlorides to be used as starting materials in the processes (c) and (d) according to the invention for preparing the compounds of the formula (I). In the formula (VI), R1 and R2 each preferably or in particular have that meaning which has already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for R1 and R2.
The sulphonyl chlorides of the formula (VI) have hitherto not been disclosed in the literature; as novel substances, they also form part of the subject-matter of the present application and they can be prepared as described above.
The formula (VIII) provides a general definition of the (thio)carboxamides to be used as starting materials in the process (d) according to the invention for preparing the compounds of the formula (I). In the formula (VIII), Q and R3 each preferably or in particular have that meaning which has already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Q and R3.
The starting materials of the formula (VIII) are known and/or can be prepared by processes known per se (cf. EP 459244).
The formula (IX) provides a general definition of the sulphonylamino-(thio)carbonyl compounds to be used as starting materials in the process (e) according to the invention for preparing the compounds of the formula (I). In the formula (IX), Q, R1 and R2 each preferably or in particular has that meaning which has already been mentioned above, in the description of the compounds of the formula (I) according to the invention, as being preferred or as being particularly preferred for Q, R1 and R2; Z preferably represents fluorine, chlorine, bromine, C1-C4-alkoxy, phenoxy or benzyloxy, in particular represents chlorine, methoxy, ethoxy or phenoxy.
The starting materials of the formula (IX) are known and/or can be prepared by processes known per se.
The processes (a), (b), (c), (d) and (e) according to the invention for preparing the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitrites such as, for example, acetonitrile and propionitrile; amides such as, for example, dimethylformamide, dimethylacetamide and N-methylpyrrolidone and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.
Suitable reaction auxiliaries or acid acceptors for use in the processes (a), (b), (c), (d) and (e) according to the invention are all acid binders which can conventionally be used for such reactions. Preference is given to alkali metal hydroxides such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, alkali metal carbonates and alkoxides such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, furthermore basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethyl-benzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).
The reaction temperatures in the processes (a), (b), (c), (d) and (e) according to the invention can be varied within a relatively wide range. In general, the processes are carried out at temperatures between xe2x88x9220xc2x0 C. and +150xc2x0 C., preferably at temperatures between 0xc2x0 C. and +100xc2x0 C.
The processes (a), (b), (c), (d) and (e) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
For carrying out the processes (a), (b), (c), (d) and (e) according to the invention, the starting materials which are required in each case are generally employed in approximately equimolar amounts. However, it is also possible to employ a relatively large excess of one of the components used in each case. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a number of hours at the respective temperature required. Work-up in the processes (a), (b), (c), (d) and (e) according to the invention is in each case carried out by customary methods (cf. the Preparation Examples).
If required, salts can be prepared from the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, such as, for example, methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding a suitable base. The salts can then be isolatedxe2x80x94if appropriate after prolonged stirringxe2x80x94by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoca, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleurn, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for the control of weeds in perennial crops for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable in particular for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonouscrops, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Suitable liquid solvents are essentially the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For the control of weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asularn, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, clilorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, di-camba, diclofop(-methyl), difeizoquat, diflufenican, dimefuron, dimepiperate, di-methachlor, dimethanctryn, dimethenamid, dinitramine, diphenamid, diquat, thiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), thofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-isopropyl), lamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), fluetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, iso-xaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples below.